Metallic thiacalix[4]arene complexes

ABSTRACT

The object of the invention is new complexes of derivatives of thiacalix[4]arenes having the formula:  
                 
 
     R 1a , R 2a , R 3a , R 4a , R 1b , R 2b , R 3b  et R 4b  are such as defined in claim 1 and their utilization, especially for manufacturing of materials having optical limiter properties.

[0001] The present invention relates to novel metallic complexes ofthiacalix[4]arenes, in particular with a transition metal, as well astheir utilization, especially in the manufacture of materials havingoptical limiter properties.

[0002] Certain thiacalixarene derivatives are described in the priorart: For example, the patent application published under number WO 99 19427 can be cited, in which the derivatives of formula (A) are described:

[0003] wherein Y is a divalent bridging group, at least one of saidbridging groups being a sulfur atom, R′₃ is hydrogen, a hydrocarbylgroup or a hydrocarbyl hetero-substituted hydrocarbyl group and is aninteger at least equal to 4.

[0004] It will be noted that the sole example of compound (A) given is adodecylcalix[8]arene containing sulfur. Moreover, it is indicated thatthe derivatives of formula (A) are used as additives in lubricating oilcompositions.

[0005] Other derivatives of thiacalix[4]arene are described in theliterature: Lhotak et al describes in Tetrahedron Letters 2000, 41,9339-9344, in particular 25,27 dimethoxythiacalix[4]arene and inTetrahedron Letters 1998, 39, 8915-8918, derivatives ofthiacalix[4]arenes of formula (B):

[0006] wherein R₁₅ is an atom of hydrogen or a tert-butyl group and R₁₇is a methyl, ethyl, n-propyl or n-butyl group. In the solid phase, thesedifferent compounds form infinite chains.

[0007] One of the objects proposed by the invention is the production ofnew derivatives of thiacalix[4]arenes having in particular the followingproperties:

[0008] good electronic delocation of electrons π;

[0009] high complexing properties;

[0010] high thermal stability, which makes possible thermal treatment ofthese compounds and thus their incorporation in materials such as in avitreous matrix, for example.

[0011] These compounds are functionalized or easily functionalized,which makes it possible to modulate their properties.

[0012] The thiacalix[4]arenes according to the invention and their metalcomplexes have non-linear, third-order optical properties. It should benoted that laser technology has seen recent and rapid progress resultingin the appearance of novel compact, performance laser systems operatingat variable wavelengths. Also, elaboration of novel materials isnecessary that make it possible to safeguard equipment, optical sensorsand the operator's eyes against the harmful effects of lasers.

[0013] Certain complexes of the thiacalix[4]arenes according to theinvention with a transition metal have thermochrome properties.

[0014] The present invention concerns the thiacalix[4]arenes having theformula (I):

[0015] wherein:

[0016] Being the same or different, R_(1a), R_(2a), R_(3a) et R_(4a)each independently being:

[0017] a hydrogen atom;

[0018] a (C₁-C₁₂) alkyl group:

[0019] a (C₁-C₁₂) alcenyl group;

[0020] an SO₂—R₁ group, wherein R₁ is a phenyl, benzyl or naphthylgroup, singly or multiply substituted or unsubstituted by a halogenatom, a (C₁-C₄) alkyl, (C₁-C₄) alcenyl or (C₁-C₄) alcynyl group, or even

[0021] a SiR₂R₃R₄ group, wherein R₂, R₃ and R₄ each independently is a(C₁-C₄) alkyl group;

[0022] R_(1b), R_(2b), R_(3b) et R_(4b), being the same or different,each being independently:

[0023] an atom of hydrogen;

[0024] a halogen atom;

[0025] a (C₁-C₆) alkyl group:

[0026] a phenylazo group, eventually preferably substituted at position4 by a nitro group;

[0027] a —N═CHR₅ group, wherein R₅ is a (C₁-C₄) alkyl, pyridyl or phenylgroup;

[0028] a —C≡C—R₆ group, wherein R₆ is a hydrogen atom, a (C₁-C₄) alkyl,tri-(C₁-C₄)-alkylsilyl, phenyl group, or a group having the formula:

[0029] wherein R′₆ is a hydrogen atom a phenyl eventually substituted inpara by a (C₁-C₆) alkyl group;

[0030] a nitro group, or even

[0031] a —NR₇R₈ group, wherein R₇ is a hydrogen atom and R₈ is ahydrogen atom or a —C(O)R₅ group with R₅ chosen from the groupcomprising (C₁-C₄) alkyl, pyridyl or phenyl;

[0032] it being understood that, when at least one of the R_(1a),R_(2a), R_(3a) and R_(4a) groups is a methyl group, the others are ahydrogen atom or when R_(1a)R_(2a)=R_(3a)=R_(4a) and is either a (C₂-C₄)alkyl or a hydrogen atom, then one at least of the substituents R_(1b),R_(2b), R_(3b) or R_(4b) is different from hydrogen or from thetert-butyl group;

[0033] as well as their salts, solvates and hydrates.

[0034] An alkyl is defined as a monovalent linear or branched saturatedhydrocarbon radical.

[0035] An alcenyl is defined as a monovalent linear or branchedunsaturated hydrocarbon radical comprising a double bond.

[0036] An alcynyl is defined as a monovalent linear or branchedunsaturated hydrocarbon radical comprising a triple bond.

[0037] A (C₁-C₄) alkyl is defined as an alkyl radical comprising from 1to 4 carbon atoms.

[0038] A halogen atom is defined as an atom of chlorine, bromine, iodineor fluorine.

[0039] It will be noted that the exclusion introduced in the definitionof the compounds having formula (I) has the particular purpose ofexcluding the compounds already described in the prior art; that is, inTetrahedron Letters 1998, 39, 8915-8918 and 2000, 41, 9339-9344.

[0040] According to another of its aspects, the present invention isrelated to the compounds of formula (I), in which:

[0041] —R_(1a), R_(2a), R_(3a) et R_(4a), being the same or different,each being independently:

[0042] a hydrogen atom;

[0043] a (C₁-C₁₂) alkyl group;

[0044] a (C₁-C₁₂) alcenyl group, or

[0045] a —SiR₂R₃R₄ group, wherein R₂, R₃ and R₄ each independently is a(C₁-C₄) alkyl group;

[0046] R_(1b), R_(2b), R_(3b) and R_(4b), being the same or different,each independently is

[0047] a hydrogen atom

[0048] a halogen atom

[0049] a (C₁-C₆) alkyl group;

[0050] a —N═CHR₅ group, in which R₅ is a (C₁-C₄) alkyl, pyridyl orphenyl group;

[0051] a —C≡C—R₆ group, in which R₆ is a hydrogen atom; a (C₁-C₄) alkyl,tri(C₁-C₄)alkylsilyl, phenyl group or a group having the formula:

[0052] where R₆′ is a hydrogen atom or a phenyl possibly with a parasubstitution with a (C₁-C₆) alkyl group;

[0053] a nitro group, or

[0054] a —NR₇R₈ group, in which R₇ is a hydrogen atom and R₈ is ahydrogen atom or a —C(O)R₅ group with R₅ being chosen from the groupcomprising a (C₁-C₄) alkyl, pyridyl or phenyl group;

[0055] it being understood that, when one at least of the groups R_(1a),R_(2a), R_(3a) or R_(4a) groups is a methyl group, the others are ahydrogen atom or when R_(1a)=R_(2a)=R_(3a)=R_(4a) and is either a(C₂-C₄) alkyl group or a hydrogen atom, when one at least of the R_(1b),R_(2b), R_(3b) or R_(4b) substituents is different from hydrogen or fromthe tert-butyl group.

[0056] as well as their salts, solvates and hydrates.

[0057] According to another of its aspects, the present invention isrelated to the compounds of formula (I), in which:

[0058] R_(1a), R_(2a), R_(3a) et R_(4a), being the same or different,each is independently:

[0059] a hydrogen atom

[0060] a (C₁-C₆) alkyl group;

[0061] a —SO₂—R₁ group, in which R₁ is a phenyl group, substituted orunsubstituted by a (C₁-C₄) alkyl group, or

[0062] a —SiR₂R₃R₄ group, in which R₂, R₃ et R₄ each independently is a(C₁-C₄) alkyl group;

[0063] R_(1b), R_(2b), R_(3b) et R_(4b), being the same or different,each independently is

[0064] a hydrogen atom

[0065] a halogen atom

[0066] a (C₁-C₆) alkyl group;

[0067] a phenylazo group possibly substituted preferably at position 4by a nitro group;

[0068] a —N═CHR₅ group, in which R₅ is a pyridyl group;

[0069] a —C≡C—R₆ group, in which R₆ is a hydrogen atom or a phenylgroup, or a group having the formula:

[0070] where R₆′ is a hydrogen atom or a phenyl possibly with a parasubstitution with a (C₁-C₆) alkyl group;

[0071] a nitro group, or

[0072] —NR₇R₈ group, in which R₇ is a hydrogen atom and R₈ is a hydrogenatom or a benzoyl group;

[0073] it being understood that, when one at least of the groups R_(1a),R_(2a), R_(3a) and R_(4a) groups are(s) a methyl group, the others are ahydrogen atom or when R_(1a)=R_(2a)=R_(3a)=R_(4a) and are either a(C₂-C₄) alkyl group or a hydrogen atom, when one at least of the R_(1b),R_(2b), R_(3b) or R_(4b) substituents is different from hydrogen or fromthe tert-butyl group;

[0074] as well as their salts, solvates and hydrates.

[0075] The compounds having formula (I), wherein one at least of theR_(1b), R_(2b), R_(3b) et R_(4b) substituents is a —N═CHR₅, —NR₇R₈ ornitro group, in which R₇ is a hydrogen atom and R₈ is a hydrogen atom ora —C(O)R₅ group with R₅ being chosen from the group comprising a (C₁-C₄)alkyl, pyridyl or phenyl group, as well as their salts, solvates orhydrates, are an other aspect of the present invention.

[0076] The object of the present invention is likewise thethiacalix[4]arenes having the formula (Ia):

[0077] in which R_(1a), R_(2a), R_(1b) and R_(2b) are as hereinbeforedefined, as well as their salts, solvates or hydrates.

[0078] The present invention similarly utilizes the thiacalix[4]areneshaving the formula (Ia), in which R_(1a) is a hydrogen atom or a(C₁-C₁₂) alkyl or (C₁-C₁₂) alcenyl group and R_(2a) is a hydrogen atomor a (C₁-C₁₂) alkyl group, (C₁-C₁₂) alcenyl, —SO₂—R₁ group or —SiR₂R₃R₄;R₁, R₂, R₃ et R₄ being such as hereinbefore described, as well as theirsalts, solvates and hydrates.

[0079] According to another of its aspects, the invention is related tothiacalix[4]arenes having the formula (Ib):

[0080] in which R_(1a), R_(2a) and R_(1b) are such as hereinbeforedescribed for (I) and (Ia), as well as their salts, solvates andhydrates.

[0081] According to yet another aspect, the invention concerns thederivatives of thiacalix[4]arenes having the formula (Ic):

[0082] in which R_(1a) and R_(1b) are such as hereinbefore described for(I) and (Ia), as well as their salts, solvates and hydrates.

[0083] The object of the present invention is likewise thethiacalix[4]arenes chosen from the group comprising:

[0084] 5,11,17,23-tetraiodo-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0085] 5,11,17,23-tetraiodo-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0086]5,11,17,23-tetra(tert-butyl)-25-propoxy-26,27,28-trihydroxythiacalix[4]arene,

[0087]5,11,17,23-tetra(tert-butyl)-25,27-di(tert-butyldimethylsiloxy)-26,28-dihydroxythiacalix[4]arene,

[0088]5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetrahexyloxythiacalix[4]arene,

[0089]5,11,17,23-tetrakis(phenylazo)-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0090]5,11,17,23-tetrakis(4-nitrophenylazo)-25,26,27,28-tetrahydroxy-thiacalix[4]arene,

[0091]5,11,17,23-tetra(tert-butyl)-25,27-di(4-toluenesulfonyloxy)-26,28-di-hydroxythiacalix[4]arene,

[0092] 5,11,17,23-tetranitro-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0093] tetrachlorhydrate of5,11,17,23-tetramino-25,26,27,28-tetrahydroxy-thiacalix[4]arene,

[0094] 25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,

[0095]25,27-di(tert-butyldimethylsiloxy)-26,28-dihydroxythiacalix[4]arene,

[0096]5,11,17,23-tetrakis(phenylazo)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,

[0097]5,11,17,23-tetrakis(4-nitrophenylazo)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,

[0098] 5,17-diiodo-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0099] 5,17-dibromo-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0100]5,11,17,23-tetra(4-pyridylimino)-25,26,27,28-tetrahydroxythiacalix[4]arene,

[0101]5,11,17,23-tetra(phenylethynyl)-25,26,27,28-tetrahydroxy-thiacalix[4]arene,

[0102]5,11,17,23-tetraethynyl-25,26,27,28-tetrahydroxy-thiacalix[4]arene.

[0103] The different conformers of the compounds having formulas (I),(Ia), (Ib) and (Ic), that is, having cone, partial cone, 1,2alternating, 1,3 alternating conformation (Tetrahedron 1999, 40,373-376) form an integral part of the invention.

[0104] Generally, the thiacalix[4]arenes according to the presentinvention can be prepared using methods similar to those used, forexample, for the synthesis of 25,26,27,28-tetrahydroxythiacalix[4]arenedescribed in particular in Tetrahedron Letters, 1998, 39, 2311-2314, orfor the synthesis of du5,11,17,23-tetra-(tert-butyl)-25,26,27,28-tetrahydroxythiacalix[4]arene,or the compounds according to the invention can be obtained by total orpartial functionalization of these known compounds utilized as startingproducts.

[0105] The compounds having formula (I) can comprise precursor groups ofother functions that are generated later in one or a plurality of steps.

[0106] The compounds having formula (I), in which R_(1a), R_(2a), R_(3a)and/or R_(4a) are different from hydrogen can be obtained usingrespective compounds, in which said R_(1a), R_(2a), R_(3a) and/or R_(4a)group(s) is a hydrogen atom by total or partial functionalization of thehydroxyl function in the presence of a base by the action, respectively,of a halogen derivative of the type Hal-R_(1a), Hal-R′_(2a), Hal-R′_(3a)and/or Hal-R′_(4a) in which Hal is a halogen atom, for example an atomof chlorine or iodine and R′_(1a), R′_(2a), R′_(3a) et R′_(4a) are,respectively, R_(1a), R_(2a), R_(3a) or R_(4a) or a precursor group ofthese latter.

[0107] In order to obtain the —O(C₁-C₁₂)alkyl functionalization, oneworks, for example, in the presence of the number of adapted equivalentsof a alkaline metal carbonate base like potassium, cesium or sodiumcarbonate in reflux acetone.

[0108] In order to obtain the —OSiR₂R₃R₄, R₂, R₃, R₄ functionalizationas defined for (I), one works in the presence of imidazole, for example.

[0109] In order to obtain the —OSO₂—R₁, R₁ functionalization as definedfor (I), one works, for example, in the presence of an amine type baselike triethylamine in reflux toluene.

[0110] The compounds (I) in which R_(1b), R_(2b), R_(3b) and/or R_(4b)are a group different from hydrogen are, for example, totally orpartially functionalized using corresponding thiacalixarene, in whichsaid R_(1b), R_(2b), R_(3b) and/or R_(4b) group(s) are hydrogen or aprecursor group of the desired function.

[0111] Details on these functionalization processes are provided in theexamples that follow.

[0112] The compounds (I) in which R_(1b), R_(2b), R_(3b) and/or R_(4b)are a derivative of the alcynyl type can be synthetized:

[0113] either when the alcynyl derivative is of the —C≡C—R₆ type, inwhich R₆ is a (C₁-C₄) alkyl, tri(C₁-C₄)alkylsilyl, phenyl group or agroup having the formula:

[0114] where R₆′ is such as hereinbefore defined for (I) using therespective compound (I), in which said R_(1b), R_(2b), R_(3b), and/orR_(4b) group(s) are a halogen atom, by the action of the H—C≡C—R₆, R₆derivative being such as hereinbefore described in the presence of tri-or diethylamine and a palladium catalyst according to the Sonogashirareaction, as described in Tetrahedron Letters 1975, 50, 4467-4470 orEur. J. Org. Chem. 2000, 3679-3681, for example;

[0115] or when the alcynyl derivative is —C≡C—H, using the respectivecompound (I), in which the R_(1b), R_(2b), R_(3b) and/or R_(4b) group(s)is a —C≡C—R₆ group, with R₆ being a tri (C₁-C₄) alkylsilyl, by theaction of potassium fluoride according to Chem. Commun. 2000, 1513-1514.

[0116] The method described by Z.-T. Huang et al in SyntheticCommunications, 1997, 27(21), 3763-3767, for the synthesis ofp-nitrocalixarenes by nitration of the corresponding calixarenes iscarried out by the action of potassium nitrate and aluminum trichloridein acetonitrile at 0° C. These operational conditions do not allow thesynthesis of compounds (I) according to the invention, in which saidR_(1b), R_(2b), R_(3b) and/or R_(4b) are a nitro group.

[0117] The action of nitrogen dioxide or dinitrogen tetroxide in thepresence of an etherized solvent been shown unexpectedly to makepossible synthesis of compounds having formula (I) comprising a nitrofunction.

[0118] Also, the object of the present invention is a method forpreparation of the compounds of formula (I), in which one at least ofthe R_(1b), R_(2b), R_(3b) or R_(4b) substituents is a nitro, —N═CHR₅,or —NR₇R₈, in which R₇ is a hydrogen atom R₈ is a hydrogen atom or a—C(O)R₅ with R₅ chosen from the group comprising a (C₁-C₄) alkyl,pyridyl or phenyl group characterized in that:

[0119] a) if R_(1b), R_(2b), R_(3b) and/or R_(4b) being a nitro group,the compound (I) is obtained by nitration of the correspondingthiacalix[4]arene, in which said R_(1b), R_(2b), R_(3b) and/or R_(4b)being a hydrogen atom, by the action of the nitrogen dioxide or thedinitrogen tetroxide in the presence of an etherize solvent;

[0120] b) if R_(1b), R_(2b), R_(3b) and/or R_(4b) is an amino group, thecompound (I) is obtained by reduction of the respective compound (I), inwhich said group(s) R_(1b), R_(2b), R_(3b) and/or R_(4b) is a nitrogroup;

[0121] c) if R_(1b), R_(2b), R_(3b) and/or R_(4b) being —N═CHR₅, R₅being a (C₁-C₄) alkyl, phenyl or pyridyl group, the compound (I) isprepared using the respective compound (I), in which said R_(1b),R_(2b), R_(3b) and/or R_(4b) are an amino group, by the action of analdehyde R₅—CHO or a ketone R₅—C(O)R₉, R₅ and R₉, being the same ordifferent, independently being one of the other, a (C₁-C₄) alkyl,pyridyl or phenyl group;

[0122] d) if R_(1b), R_(2b), R_(3b) and/or R_(4b), being a —NHC(O)R₅group, in which R₅ is a (C₁-C₄)alkyl, pyridyl or phenyl group, thecompound (I) is obtained using the respective compound (I), in whichR_(1b), R_(2b), R_(3b) and/or R_(4b) being an amino group, by the actionof the acid halogenide Hal-C(O)R₅, in which Hal is a halogen atom and R₅and is as hereinbefore defined.

[0123] For the synthesis described in a), dimerized nitrogen dioxide canbe used called dinitrogen tetroxide. This nitrogen dioxide forms acomplex with the ether used that can be, for example, of the di, tri ortetraglyme or a crown ether. Commercial nitrogen dioxide or prepared onsite is used, for example, by the action of a nitrate of the alkalinemetal nitrate type, such as potassium nitrate in the presence of a Lewisacid such as aluminum trichloride. The nitrogen dioxide/ether complexcan be synthesized in situ or previously prepared by bubbling thenitrogen dioxide in the cooled ether solvent. Reference can be made tothe Journal of Molecular Structure, 1988, 178, 135.

[0124] For the synthesis described in b), reducer pairs of thetin/hydrochloric acid or zinc/acetic acid type can be used.

[0125] For the synthesis described in c), one works preferably in anacid environment, for example in the presence glacial acetic acidaccording to the method described by Angew Chem. Int. Ed. Engl. 1996,35(5), 538-540.

[0126] For the synthesis described in d) reference can be made to J.Chem. Soc. Perkin Trans. 2, 1996, 1175.

[0127] The functional groups eventually present in the compounds havingthe formula (I), (Ia), (Ib), (Ic) and in the reaction intermediates, canbe protected either permanently or temporary by protector group thatassure proper synthesis of the expected compounds. The protection ordeprotection reactions are carried out according to the methods wellknown to the specialist in the art. The specialist in the art will becapable of choosing the appropriate protector groups.

[0128] The compounds (I) are isolated and purified using classicalseparation techniques. For example, recrystallizations or even classicalchromatographic techniques in chiral or non-chiral phase can be used.

[0129] An other object of the present invention is the complexes (II) ofcompounds of the formula (I), (Ia), (Ib) and (Ic) with a metal and inparticular a transition metal at variable degrees of oxidation. Thefollowing can be cited as examples of a transition metal: copper,palladium, mercury, gold and more preferably, silver, zinc, platinum orlead.

[0130] These complexes (II) are obtained using methods well known to thespecialist in the art, for example, by adding a metal salt to thethiacalix[4]arenes having the formula (I) in solution in an appropriateorganic solvent, for example tetrahydrofurane, chloroform or pyridine.

[0131] The complexes according to the invention are, for example,capable of being obtained by reaction of a thiacalix[4]arenes having theformula (I) with a metal derivative of the type: AgSO₃CF₃, zinc (II)chloride, copper (II) chloride, Trans-[PtCl(PEt₃)₂(C≡C-phenyl)] orTrans-{PtCl(PEt₃)₂[C≡C-(4-pentylphenyl)]} or another platinum complexcomprising another phosphine of the trialkylphosphine type and/or aphenyl group differently substituted in position 4 by another alkylgroup, this list not being in any way limiting whatsoever.

[0132] The compounds having formula (I) as well as their metal complexes(II) according to the invention have third-order non-linear opticalproperties.

[0133] The optical limitation measurements were done using a measurementbench of the same type as those previously described by: D. Vincent inNonlinear Optics 1999, 21, 413-422 et D. D. James, K. J. McEwan inNonlinear Optics, 1999, 21, 377-389. For an incident laser beam ofvariable energy (0-400 μJ) the maximal transmitted energies weremeasured varying from 100 μJ to 5 μJ for the compounds providing thebest results.

[0134] The derivatives according to the invention are thus particularlyinteresting and can be utilized especially as optical limiters. They canbe used for manufacturing materials having optical limiter properties.They can be incorporated into vitreous type matrices by using, forexample, the sol-gel (C. J. Brinker, G. W. Scherer, Sol-Gel Science. ThePhysics and Chemistry of Sol-Gel Processing, Academic Press, 1990 et L.C. Klein, Sol-Gel Optics: Processing and Applications, Kluwer AcademicPublishers, 1994) for producing materials for use as protection againstlasers.

[0135] The complexes (II) according to the invention having zinc, copperor nickel are the colored compounds that have interesting colorationproperties as a function of temperature. For example, the compound II.5(example 5B) goes from the color purple to a Bordeaux red once thetemperature reaches 25° C. This transformation is reversible and thecompound returns to its initial coloration upon cooling. The compound isstable over time and can sustain a great many cycles of color change.This was the object of a study using differential calorimetric analysis(DSC820 Mettler Toledo), which demonstrated a phase transition peak ofbetween 25 and 40° C. corresponding to the color change phenomenondescribed.

[0136] Accordingly, they can be used for manufacturing thermochromematerials.

[0137] The thiacalix[4]arenes (1) according to the invention can be usedfor water treatment, they especially make possible selective extractionof organic compounds (Chemistry Letters, 1999, 777) or cations(Tetrahedron Letters 1998, 39, 7559 and 2001, 42, 1021).

[0138] Similarly, certain thiacalix[4]arenes (I) and their metalcomplexes (II), in virtue of their second-order non-linear opticalproperties, can be used as frequency doublers (Angew Chem. Int. Ed.Engl, 1992, 31(8), 1075).

[0139] The examples that follow illustrate the invention withoutlimiting it.

[0140] The nuclear magnetic resonance (NMR) spectra were done at 300 MHzand at 25° C. and the chemical shifts are expressed in ppm. Thefollowing abbreviations are used: s=singlet, m=multiplet, d=doublet,t=triplet, sex=sextuplet.

EXAMPLES A—Thiacalix[4]arenes (I) Example 1A

[0141] 5,11,17,23-Tetraiodo-25,26,27,28-tetrahydroxythiacalix[4]arene,Compound I.1

[0142] 1 g of 25,26,27,28-tetrahydroxythiacalix[4]arene (preparedaccording to Tetrahedron Letters, 1998, 39, 2311-2314) is dissolved in60 ml of dichloromethane. 2.979 g of benzyltrimethyl ammoniumdichloroiodate are added to this solution. The orange suspension isstirred for 30 minutes and then 30 ml of methanol are added; it is thenstirred for another 30 minutes and treated with 1.62 g of calciumcarbonate. The suspension is stirred for 24 hours at room temperature.After addition of 6 ml of concentrated hydrochloric acid and 100 ml ofmethanol, the suspension is decolorized using 160 ml of an aqueoussolution of 10% sodium hydrogen sulfate, then filtered. The residue iswashed with approximately 16 ml 1M hydrochloric acid, 90 ml of water, 10ml of methanol and 50 ml of dichloromethane to produce a white solid(65% yield).

[0143] RMN¹H (δ, ppm, C₅D₅ N): 7.83 (s, 8H).

Example 2A

[0144] 5,11,17,23-Tetrabromo-25,26,27,28-tetrahydroxythiacalix[4]arene,Compound I.2

[0145] 1 g of 25,26,27,28-tetrahydroxythiacalix[4]arene is suspended in50 ml of acetone. 1.43 g of N-bromosuccinimide are added to thissuspension. The reaction mixture is mixed under nitrogen, protected fromlight and at room temperature for 24 hours. The solvents are evaporated,then the solid obtained is washed with approximately 50 ml of water, 20ml of methanol and 20 ml of dichloromethane. The light brown residueobtained is collected in 10 ml of pyridine and then precipitated usingacetonitrile in order to obtain a white powder (60% yield).

[0146] 2-butanone can be used in lieu of acetone as the solvent.

[0147] RMN¹H (δ, ppm, C₅D₅N): 7.83 (s, 8H); 12.34 (s, 4H).

Example 3A

[0148]5,11,17,23-Tetra(tert-butyl)-25-propoxy-26,27,28-trihydroxythiacalix[4]arene,Compound I.3

[0149] 30 g of5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetrahydroxythiacalix[4]arene(prepared according to Tetrahedron Letters, 1997, 38(22), 3972-3972) aresuspended in 20 ml of acetone and 0.191 g of potassium hydrogencarbonate are added. The suspension is reflux mixed under inertatmosphere for approximately 30 minutes and then 0.16 ml of n-propyliodide are added. The suspension is reflux stirred for approximately 24hours; then the solvents are evaporated. The residue is collected in 90ml of dichloromethane and acidified using 30 ml of 1M hydrochloric acid.The organic phase is washed using 30 ml of saturated sodium chloridesolution and twice with 30 ml of water and then dried over sodiumsulfate. The organic phase is concentrated and then precipitated usingmethanol. The yellow powder obtained is recrystallized in achloroform/methanol mixture in order to produce colorless crystals (60%yield).

[0150] RMN¹H (δ, ppm, CDCl₃): 0.80 (s, 9H); 1.16 (t, 3H); 1.22 (s, 9H);1.34 (s, 18H) 2.06 (sex, 2H); 4.45 (t, 2H); 6.96 (s, 2H); 7.66 and 7.64(s, 4H); 7.97 (s, 2H).

Example 4A

[0151]5,11,17,23-Tetra(tert-butyl)-25,27-di(tert-butyldimethylsiloxy)-26,28-dihydroxythiacalix[4]arene,Compound I.4

[0152] 0.5 g de5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetrahydroxythiacalix[4]areneare dissolved in 40 ml of dichloromethane. 0.1 g of imidazole and 1.255g chloride of tert-butyldimethylsilane are added to the solution. Thesolution is stirred for approximately 24 hours at room temperature andthen acidified using 40 ml of 1M hydrochloric acid. The organic phase iswashed using 30 ml of saturated sodium chloride solution and twice with30 ml of water and then dried over sodium sulfate. The organic phase isconcentrated and then precipitated using methanol. The product obtainedcan then be recrystallized in a chloroform/methanol mixture in order toprovide a white powder (90% yield).

[0153] RMN¹H (δ, ppm, CDCl₃): 0.33 (s, 12H); 0.85 (s, 18H); 1.19 (s,18H); 1.31 (s, 18H); 7.06 (s, 4H); 7.62 (s, 4H).

Example 5A

[0154]5,11,17,23-Tetra(tert-butyl)-25,26,27,28-tetrahexyloxythiacalix[4]arene,Compound I.5

[0155] 0.73 g of5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetrahydroxythiacalix[4] aresuspended in 50 ml of acetone. 2.768 g potassium carbonate are added tothe mixture that is heated to reflux and under inert atmosphere untilclarification. 3 ml of 1-iodohexane are added. The mixture is heated toreflux for approximately 24 hours. The solvents are evaporated underreduced pressure then the residue obtained is collected in 50 ml ofchloroform. This organic phase is then washed with approximately 40 mlof 1M hydrochloric acid, 40 ml of saturated sodium chloride solution and2 times with 40 ml of water. The organic phase is dried over sodiumsulfate and then the solvents are evaporated under reduced pressure. Thecrude powder is recrystallized in a chloroform/methanol mixture in orderto produce a white powder (65% yield).

[0156] RMN¹H (δ, ppm, CDCl₃): 0.85 (t, 12H); 0.99 to 1.14 (m, 32H); 1.27(s, 36H); 3.81 (t, 8H); 7.30 (s, 8H).

Example 6A

[0157]5,11,17,23-Tetrakis(phenylazo)-25,26,27,28-tetrahydroxythiacalix[4]arene,Compound I.6

[0158] a) Tetrafluoroborate of Benzene Diazonium

[0159] 4.55 ml of aniline are added to 12.6 ml of concentratedhydrochloric acid and 3.65 g of sodium nitrite at a temperature of 0° C.A solution of 7.6 g of sodium tetrafluoroborate in 15 ml of water isadded. The white precipitate formed is filtered, then washed with 5 mlof iced water, 3 ml of ethanol and 5 ml of diethyl ether. The product isthen dried on filter paper for 13 hours (yield 70%).

[0160] b) 0.5 g of 25,26,27,28-tetrahydroxythiacalix[4]arene and 1.6 gof benzene diazonium tetrafluoroborate are dissolved in 20 ml oftetrahydrofurane. 1 ml of pyridine is added at 0° C. to and the reactionmixture is stirred for 16 hours at room temperature, then 50 ml ofmethanol are added in order to obtain a yellow precipitate. Theprecipitate obtained is washed, successively, in methanol and diethylether and recrystallized in a pyridine methanol mixture (64% yield).

[0161] RMN¹H (δ, ppm, C₅D₅N) 7.32 (t, 4H); 7.41 (t, 8H); 7.90 (d, 8H);8.54 (s, 8H); 14.6 (s, 4H).

Example 7A

[0162]5,11,17,23-Tetrakis(4-nitrophenylazo)-25,26,27,28-tetrahydroxythiacalix[4]arene,Compound I.7

[0163] a) Tetrafluoroborate of 4-nitrobenzene Diazonium

[0164] 17 g or 4-nitroaniline are dissolved heated in 65 ml of 6Mhydrochloric acid. After cooling the mixture to 0° C., 9 g or sodiumnitrite, then 20 g of sodium tetrafluoroborate are added. Theprecipitate is filtered and added successively with an aqueous solutionof 5% sodium tetrafluoroborate, ethanol and diethyl ether. Finally, theproduct is dried on filter paper (97% yield).

[0165] b) 0.35 g of 25,26,27,28-tetrahydroxythiacalix[4]arene and 1.4 gof 4-nitrobenzene diazonium tetrafluoroborate are dissolved in 20 ml oftetrahydrofurane. 1 ml of pyridine is added at 0° C. The reactionmixture becomes orange and a light precipitate appears. After two days,the precipitate is filtered and washed successively with coldtetrahydrofurane and methanol. The precipitate obtained isrecrystallized in the pyridine in order to produce red crystals.

[0166] RMN ¹H (δ, ppm, C₅D₅N): 8.17 (s, 4H); 8.29 and 7.86 (2d, 2×8H);8.60 (s, 8H).

Example 8A

[0167]5,11,17,23-Tetra(tert-butyl)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,Compound I.8

[0168] 0.5 g of5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetrahydroxythiacalix[4]areneare dissolved in 20 ml of toluene in reflux under nitrogen atmosphere.0.926 g of 4-toluene sulfonyl chloride and 1.5 ml of triethylamine areadded to the reaction mixture. The reaction mixture is reflux heated for6 hours then slowly cooled to room temperature. The solvents areevaporated and the brown residue obtained is collected with 40 ml ofdichloromethane, washed three times with 30 ml 1N hydrochloric acid andfour times with 30 ml of water, then dried over sodium sulfate. Afterfiltration, evaporation of the solvents and addition of methanol, awhite powder precipitates. The powder obtained is recrystallized in adichloromethane/methanol mixture. (73% yield).

[0169] RMN ¹H (δ, ppm, CDCl₃): 1.29 and 0.84 (s, 36H); 2.49 (s, 6H);7.01 (s, 4H); 7.60 (s, 4H); 7.86 and 7.36 (d, 8H)

Example 9A

[0170] 5,11,17,23-Tetranitro-25,26,27,28-tetrahydroxythiacalix[4]arene,Compound I.9

[0171] 0.6 g of 25,26,27,28-tetrahydroxythiacalix[4]arene are suspendedin 20 ml of diethylene glycol dimethyl ether (diglyme), 0.9 g ofpotassium nitrate and 3.16 g of aluminum trichloride are added to thesuspension. The reaction is gently activated by heating until theappearance of a brown color, then stirred for 12 hours at roomtemperature. The suspension is hydrolyzed with 90 ml of water. Theorganic phase is extracted with 2 times 30 ml of ethyl acetate. The 2organic fractions are combined and then dried over sodium sulfate. Thesolvents are evaporated under reduced pressure, then a precipitate isobtained using approximately 50 ml of diethyl ether. The powder obtainedis purified by chromatography over a silica gel column by eluating witha chloroform/methanol mixture, 7/3 (v/v) in order to produce a yellowsolid (35% yield).

[0172] RMN ¹H (δ, ppm, CD₃CN): 8.44 (s, 4H).

Example 10A

[0173] Tetrachlorhydrate of5,11,17,23-tetramino-25,26,27,28-tetrahydroxythiacalix[4]arene, CompoundI.10

[0174] 0.5 g of compound 1.9 is suspended in 20 ml of concentratedhydrochloric acid. 2 g of metallic tin are added to this suspension. Thereaction mixture is reflux heated for 1 hour. The white suspension iscooled in an ice bath and then filtered. The white precipitate is washedwith cold hydrochloric acid and then with diethyl ether (quantitativeyield).

[0175] RMN ¹H (δ, ppm, (CD₃)₂SO): 7.44 (s, 8H); 9.92 (s, 4H).

Example 11A

[0176] 25,27-Di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,Compound I.11

[0177] Prepared according to operational method described in EXAMPLE 8A,using 25,26,27,28-tetrahydroxythiacalix[4]arene.

Example 12A

[0178]25,27-Di(tert-butyldimethylsiloxy)-26,28-dihydroxythiacalix[4]arene,Compound I.12

[0179] Prepared according to the same operational method described inEXAMPLE 4A, using 25,26,27,28-tetrahydroxythiacalix[4]arene.

[0180] RMN ¹H (δ, ppm, CDCl₃): 0.33 (s, 12H); 1.15 (s, 18H); 6.07 (d,4H); 6.43 (t, 2H); 6.79 (t, 2H); 7.60 (d, 4H)

Example 13A

[0181]5,11,17,23-Tetrakis(phenylazo)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,Compound I.13

[0182] Prepared according to the operational method described in EXAMPLE8A, using compound 1.6.

Example 14A

[0183]5,11,17,23-Tetrakis(4-nitrophenylazo)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene,Compound I.14

[0184] Prepared according to the operational method described in EXAMPLE8A, using compound 1.7.

Example 15A

[0185] 5,17-Diiodo-25,26,27,28-tetrahydroxythiacalix[4]arene, CompoundI.15

[0186] Prepared by forming the intermediate5,17-diiodo-25,27-di(tert-butyldimethylsiloxy)-26,28-dihydroxythiacalix[4]areneaccording to the operational method described in EXAMPLE 1A usingcompound 1.12 and 2.1 equivalents of benzyl trimethyl ammoniumdichloroiodate, which is then treated with potassium fluoride in thepresence of crown ether (18-crown-6) (G. Stork, P. F. Hudrlik, J. Am.Chem. Soc., 60, 4462, 1968; C. L. Liotta, P. H. Harris, J. Am. Chem.Soc., 96, 2250, 1974) or with tetrabutyl ammonium fluoride intetrahydrofurane (E. J. Corey, A. Venkateswarlu, J. Am. Chem. Soc, 94,6190, 1972).

Example 16A

[0187] 5,17-Dibromo-25,26,27,28-tetrahydroxythiacalix[4]arene, CompoundI.16

[0188] Prepared according to the operational method described in EXAMPLE15A, using 2.1 equivalents of N-bromosuccinimide.

[0189] The EXAMPLES according to the invention are presented in TABLE 1,below. TABLE 1 (I)

EXAMPLES R_(1a) R_(3a) R_(2a) R_(4a) R_(1b) R_(3b) R_(2b) R_(4b) 1AR_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b) = R_(4b)= I 2A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b) =R_(4b) = Br 3A —(CH₂)₂CH₃ R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(2b) =R_(3b) = R_(4b) = —C(CH₃)₃ 4A R_(1a) = R_(3a) = — R_(2a) = R_(4a = H)R_(1b) = R_(2b) = R_(3b) = R_(4b) = —C(CH₃)₃ Si(CH₃)₂[C(CH₃)₃] 5A R_(1a)= R_(2a) = R_(3a) = R_(4a) = —(CH₂)₅CH₃ R_(1b) = R_(2b) = R_(3b) =R_(4b) = —C(CH₃)₃ 6A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H

7A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H

8A

R_(2a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b) = R_(4b) = —C(CH₃)₃ 9AR_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b) = R_(4b)= —NO₂ 10A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(2b) =R_(3b) = R_(4b) = —NH₃ ⁺, Cl⁻ 11A

R_(2a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b) = R_(4b) = H 12A R_(1a) =R_(3a) = —Si(CH₃)₂[C(CH₃)₃] R_(2a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b)= R_(4b) = H 13A

R_(2a) = R_(4a) = H

14A

R_(2a) = R_(4a) = H

15A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(3b) = I R_(2b) =R_(4b) = H 16A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(3b) =Br R_(2b) = R_(4b) = H 17A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H

18A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H

19A R_(1a) = R_(2a) = R_(3a) = R_(4a) = n − propyl R_(1b) = R_(2b) =R_(3b) = R_(4b) = Br 20A R_(1a) = R_(2a) = R_(3a) = R_(4a) = n − propylR_(1b) = R_(2b) = R_(3b) = R_(4b) = I 21A R_(1a) = R_(2a) = R_(3a) =R_(4a) = n − propyl R_(1b) = R_(2b) = R_(3b) = R_(4b) = —C≡C—Si(CH₃)₃22A R_(1a) = R_(2a) = R_(3a) = R_(4a) = n − propyl R_(1b) = R_(2b) =R_(3b) = R_(4b) = —C≡C—H 23A R_(1a) = R_(2a) = R_(3a) = R_(4a) = n −propyl

24A R_(1a) = R_(2a) = R_(3a) = R_(4a) = n − propyl

25A R_(1a) = R_(2a) = R_(3a) = R_(4a) = n − propyl

26A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H R_(1b) = R_(2b) = R_(3b) =R_(4b) = —C≡C—H 27A R_(1a) = R_(2a) = R_(3a) = R_(4a) = H

Example 19A

[0190] 5,11,17,23-Tetrabromo-25,26,27,28-tetrapropoxythiacalix[4]areneCompound I.19

[0191] 1 g of5,11,17,23-tetrabromo-25,26,27,28-tetrahydroxythiacalix[4]arene(compound 1.2) is suspended in 60 ml of acetone. 3.2 g of cesiumcarbonate are added to this suspension. The mixture is reflux heatedunder nitrogen until clearing and then 1.2 ml of 1-iodopropane areadded. The mixture is heated to reflux for approximately 24 hours. Thesolvents are evaporated under reduced pressure; then the residueobtained is collected in 90 ml of chloroform. The organic phase is thenwashed with approximately 40 ml of 1M hydrochloric acid and 2×40 ml ofwater. The organic phase is dried over sodium sulfate and then thesolvents are evaporated under reduced pressure. The crude powder ispurified by chromatography over silica (silica, 2 CHCl₃/8 hexane)-80%yield.

Example 20A

[0192]5,11,17,23-tetraiodo-25,26,27,28-tetrapropoxythiacalix[4]arene(2),Compound I.20

[0193] 1 g of5,11,17,23-tetraiodo-25,26,27,28-tetrahydroxythiacalix[4]arene (compound1.1) is suspended in 60 ml of acetone. 2.6 g of cesium carbonate areadded to this suspension. The mixture is reflux heated under nitrogenuntil clearing and then 1 ml of 1-iodopropane are added. The mixture isreflux heated for approximately 24 hours. The solvents are evaporatedunder reduced pressure; then the residue obtained is collected in 90 mlof chloroform. The organic phase is then washed with approximately 40 mlof 1M hydrochloric acid and 2×40 ml of water. The organic phase is driedover sodium sulfate and then the solvents are evaporated under reducedpressure. The crude powder is purified by chromatography over silica(silica, 2 chloroform/8 hexane)-75% yield.

Example 21A

[0194]5,11,17,23-tetratrimethylsilylethynyl-25,26,27,28-tetrapropoxythiacalix[4]arene(3), Compound I.21

[0195] Approach 1:

[0196] 0.5 g of5,11,17,23-tetraiodo-25,26,27,28-tetrapropoxythiacalix[4]arene (compoundI.20) are suspended in 20 ml of deoxygenated triethylamine. 30 mg ofdichloro-bis-triphenyl phosphine palladium (II), 4 mg of cupreous iodideand 0.2 g of trimethylsilyl acetylene are added to this suspension. Thereaction mixture is heated to 40° C. for 24 hours, then treated with HCl(10%) and extracted using 40 ml of ethyl acetate.

[0197] The organic phase is washed with water (2×30 ml) then dried overNa₂SO₄. Finally, the product is purified by chromatography over a column(silica 8 hexane/2 chloroform)-75% yield.

[0198] Approach 2:

[0199] 0.5 g of5,11,17,23-tetrabromo-25,26,27,28-tetrapropoxythiacalix[4]arene(compound I.19) is suspended in 20 ml of deoxygenated triethylamine. 30mg of dichloro-bis-triphenyl phosphine palladium (II), 5 mg of cupreousiodide and 0.25 g of trimethylsilyl acetylene are added to thissuspension. The reaction mixture is heated to 40° C. for 24 hours, thentreated with HCl (10%) and extracted using 40 ml of ethyl acetate.

[0200] The organic phase is washed with water (2×30 ml) then dried overNa₂SO₄. Finally, the product is purified by chromatography over a column(silica 8 hexane/2 chloroform)-70% yield.

Example 22A

[0201]5,11,17,23-Tetraethynyl-25,26,27,28-tetrapropoxythiacalix[4]arene,Compound I.22

[0202] 0.5 g of5,11,17,23-tetratrimethylsilylethynyl-25,26,27,28-tetrapropoxythiacalix[4]arene(compound I.21) is dissolved in 20 ml of tetrahydrofurane. 1.2 g offluoride of tetrabutyl ammonium trihydrate are added. The solution isstirred for 2 h under inert atmosphere, then evaporated to dryness. Theresidue is collected in chloroform. The organic phase is washed withHCl.

[0203] 1 M, then H₂O and dried over Na₂SO₄. After evaporation of thesolvents, the product is purified by chromatography over a column(silica, 8 hexane/2 chloroform)-90% yield.

[0204] Compose 23A

[0205]5,11,17,23-Tetraphenylethynyl-25,26,27,28-tetrapropoxythiacalix[4]arene,Compound I.23

[0206] 0.5 g of5,11,17,23-tetraiodo-25,26,27,28-tetrapropoxythiacalix[4]arene issuspended in 20 ml of triethylamine in the absence of oxygen. 20 mg ofdichloro-bis-triphenyl phosphine palladium (II), 4 mg of cupreous iodideand 0.2 g of phenyl acetylene are added to this suspension. The reactionmixture is heated to 40° C. for 24 hours, then treated with HCl (10%)and extracted using 40 ml of ethyl acetate; the organic phase is washedwith water (2×30 ml) then dried over Na₂SO₉. Finally, the product ispurified by chromatography over a column (silica 8 hexane/2 chloroform).

Example 24A

[0207] Compound I.24

[0208] 0.24 g or 2-iodo-5-(phenylethynyl) thiophene are suspended in 20ml of triethylamine in the absence of oxygen. 30 mg ofdichloro-bis-phenyl phosphine palladium (II), 0.004 g of cupreous iodideand 0.125 g of5,11,17,23-tetraethynyl-25,26,27,28-tetrapropoxythiacalix[4]arene(compound I.22). The reaction mixture is heated to 40° C. for 24 hours,then treated with HCl (10%) and extracted using 40 ml of ethyl acetate;the organic phase is washed with water (2×30 ml) then dried over Na₂SO₄.Finally, the product is purified by chromatography over a column (8hexane/2 CHCl₃).

[0209] A similar compound is also prepared using compound I 22 and2-iodo-5 [(4-pentylphenyl)ethynyl]thiophene.

B—Complexes (H) Examples 1B

[0210] Complex of Compound I.6 with AgSO₃CF₃: Ag₄[I.6]⁴⁺ Compound II.1

[0211] 0.1 g of compound 1.6 is dissolved in 10 ml of chloroform. 0.1 gof AgSO₃CF₃ are added to the solution and then the reaction mixture isstirred for approximately 12 hours at room temperature and away fromlight. After filtration, the red powder obtained is washed with methanoland diethyl ether.

[0212] Elementary Microanalysis Ag₄[1.6] (SO₃CF₃)₄, C₅H₅N

[0213] Found: C 34.07% N 6.20% H 1.82% S12.49% Ag 22.41%

[0214] Calculated: C 33.98% N 6.24% H 1.83% S 12.68% Ag 21.37%.

Example 2B

[0215] Complex of Compound I.6 with ZnCl₂: Zn[I.6]₂ ²⁺ Compound II.2

[0216] 0.1 g of compound I.6 is dissolved in achloroform/tetrahydrofurane 10/1 (v/v) mixture. 0.1 g of zinc (II)chloride and 0.2 ml of pyridine are added to this orange-coloredsolution. The solution is stirred for 48 hours at room temperature. Theyellow suspension is filtered. The yellow powder obtained is washed withwater, methanol and diethyl ether.

[0217] Elementary Microanalysis Zn[I.6]₂Cl₂,C₅H₅N

[0218] Found:C 57.06% N 11.29% H 3.39% S 11.94% Zn 3.57%

[0219] Calculated:C 60.00% N 11.89% H 3.49% S 12.00% Zn 3.08%.

Example 3B

[0220] Complex of Compound I.6 with CuCl₂: Cu₄[I.6]⁴⁺ Compound II.3

[0221] 0.1 g of compound 1.6 is dissolved in 10 ml of chloroform. 0.063g of copper (II) chloride are added to this solution. The suspension isstirred for 24 hours at room temperature. The suspension is filtered,then the solvents are evaporated. The brown colored powder is washed inmethanol, in water and in diethyl ether.

[0222] Elementary Microanalysis Cu₄[I.6]Cl₈,C₅H₅N

[0223] Found:C 43.87% N 7.86% H 2.90% S 8.71% Cu 16.77%

[0224] Calculated:C 41.50% N 8.20% H 2.41% S 8.36% Cu 16.61%.

Example 4B

[0225] Complex of Compound I.7 with AgSO₃CF₃: Ag₅[I.7]₂ ⁵⁺ Compound II.4

[0226] 0.15 g of compound I.7 is dissolved in 20 ml of pyridine. 0.1 gof AgSO₃CF₃ are added and then the reaction mixture is stirred forapproximately 24 hours at room temperature and away from light. It isprecipitated with methanol; the violet powder obtained is washed inmethanol and in diethyl ether.

[0227] Elementary Microanalysis Ag₅[I.7]₂(SO₃CF₃)₅, 13C₅H₅N

[0228] Found:C 46.07% N 12.62% H 2.38% S 9.22% Ag 12.14% Calculated:C44.30% N 11.52% H 2.69% S 9.25% Ag 11.99%.

Example 5B

[0229] Complex of Compound I.7 with ZnCl₂: Zn[I.7]₂ ⁺² Compound II.5

[0230] 0.1 g of compound I.7 is suspended in 10 ml of tetrahydrofurane.0.1 g of zinc (II) chloride and 0.9 ml of water are added to thissuspension. The suspension is stirred for 69 hours at room temperature.The suspension is filtered. The filtrate is concentrated and thenprecipitated with methanol. The purple powder obtained is washed inmethanol, in water and in diethyl ether.

[0231] Elementary Microanalysis Zn[I.7]₂Cl₂

[0232] Found:C 48.09% N 12.63% H 2.68% S 9.14% Zn 3.29%

[0233] Calculated:C 49.60% N 14.47% H 2.41% S 11.00% Zn 2.81%.

[0234] The deviations obtained among the calculated and experimentalresults of the elementary analysis are attributable to the presence ofsolvatation molecule.

Example 6B

[0235] Complexes of Platinum with Compound I.22: Compound II.6 Havingthe Formula:

[0236] where R=n-propyl

[0237] 0.1 g of trans —[PtCl(PEt₃)₂(C≡C-phenyl)] is dissolved in a 1toluene/1 diethylamine mixture. 0.0003 g of cupreous chloride and then asolution of 0.028 g of5,11,17,23-tetraethynyl-25,26,27,28-tetrapropoxythiacalix[4]arene(compound 22.1) in 10 ml of toluene are added to this solution. Thereaction mixture is stirred at room temperature for 24 hours, evaporatedto dryness and collected in dichloromethane. The organic phase is driedon magnesium sulfate and then evaporated to dryness. The residue ispurified by chromatography over basic alumina. A complex analogous tocompound II.6 using trans-—{PtCl(PEt₃)₂[C≡C-(4-pentylphenyl)]} was alsoprepared using the same operational method.

[0238] Complexes analogous to compound II.6, in which R=methyl or—C₂H₄O₂CNHC₂H₄Si(OEt)₃, were also prepared using the same operationalmethod.

Example 7B

[0239] Complexes of Platinum with Compound I.25: Compound II.7 Havingthe Formula:

[0240] This complex is prepared using the same operating method as thatof EXAMPLE 6B. A complex analogous to compound II.7 using trans—{PtCl(PEt₃)₂[C≡C-(4-pentylphenyl)]} was also prepared using the sameoperational method.

[0241] Complexes analogous to compound II.7, in which R=methyl or—C₂H₄O₂CNHC₂H₄Si(OEt)₃, were also prepared using the same operationalmethod.

1- Metal (II) complexes with a thiacalix[4]arene, possibly in the form of a salt, solvate or hydrate, having the formula (I):

wherein: R_(1a), R_(2a), R_(3a) et R_(4a), being the same or different, each is independently: a hydrogen atom; a (C₁-C₁₂) alkyl group; a (C₁-C₁₂) alcenyl group; a —SO₂—R₁ group, in which R₁ is a phenyl, benzyl or naphthyl group, substituted or unsubstituted one or more times with a halogen atom, a (C₁-C₄) alkyl group, (C₁-C₄) alcenyl group or (C₁-C₄) alcynyl group, or a—SiR₂R₃R₄, in which R₂, R₃ et R₄ each independently being a (C₁-C₄) alkyl group; R_(1b), R_(2b), R_(3b) et R_(4b), being the same or different, each independently being: a hydrogen atom; a halogen atom; a (C₁-C₆) alkyl group; a phenylazo group eventually substituted preferably in position 4 by a nitro group; a —N═CHR₅ group, in which the R₅ is a (C₁-C₄) alkyl, pyridyl or phenyl group; a —C≡C—R₆ group, in which R₆ is a hydrogen atom; a (C₁-C₄) alkyl, tri(C₁-C₄) akylsilyl, or phenyl group; a nitro group, or a —NR₇R₈ group, in which R₇ is a hydrogen atom and R₈ is a hydrogen atom or a —C(O)R₅ group with R₅ being chosen from a (C₁-C₄) alkyl, pyridyl or phenyl group; it being understood that, when at least one of the R_(1a), R_(2a), R_(3a) et R_(4a) groups is a methyl group, the others are a hydrogen atom or when R_(1a)=R_(2a)=R_(3a)=R_(4a) and are either a (C₂-C₄) alkyl or a hydrogen atom, then the at least one of the R_(1b), R_(2b), R_(3b) or R_(4b) substituents is different from hydrogen or from the tert-butyl group. 2- Metal (II) complexes with a thiacalix[4]arene, possibly in the form of a salt, solvate or hydrate, having the formula (I):

wherein: R_(1a), R_(2a), R_(3a) et R_(4a), being the same or different, each is independently: a hydrogen atom; a (C₁-C₁₂) alkyl group; a (C₁-C₁₂) alcenyl group; a —SO₂—R₁ group, in which R₁ is a phenyl, benzyl or naphthyl group, substituted or unsubstituted one or more times with a halogen atom, a (C₁-C₄) alkyl group, (C₁-C₄) alcenyl group or (C₁-C₄) alcynyl group, or a —SiR₂R₃R₄, in which R₂, R₃ et R₄ each independently being a (C₁-C₄) alkyl group; R_(1b), R_(2b), R_(3b) and R_(4b), being the same or different, each independently being: a hydrogen atom; a halogen atom; a (C₁-C₆) alkyl group; a phenylazo group, eventually substituted preferably at position 4 with a nitro group; a —N═CHR₅ group, in which the R₅ is a (C₁-C₄) alkyl, pyridyl or phenyl group; a —C≡C—R₆ group, in which R₆ is a hydrogen atom, a (C₁-C₄) alkyl, tri (C₁-C₄) alkylsilyl, phenyl group, or a group having the formula:

where R′₆ is a hydrogen atom or a phenyl, eventually substituted in para by a (C₁-C₆) alkyl group; a nitro group, or a —NR₇R₈ group, in which R₇ is a hydrogen atom and R₈ is a hydrogen atom or a —C(O)R₅ group with R₅ being chosen from a (C₁-C₄) alkyl, pyridyl or phenyl group; it being understood that, when at least one of the R_(1a), R_(2a), R_(3a) et R_(4a) groups is a methyl group, the others are a hydrogen atom or when R_(1a)=R_(2a)=R_(3a)=R_(4a) and are either a (C₂-C₄) alkyl or a hydrogen atom, then the at least one of the R_(1b), R_(2b), R_(3b) or R_(4b) substituents is different from hydrogen or from the tert-butyl group. 3- Metal (II) complexes according to claim 1, wherein: R_(1a), R_(2a), R_(3a) and R_(4a), being the same or different, each is independently: a hydrogen atom; a (C₁-C₁₂) alkyl group; a (C₁-C₁₂)alcenyl group, or a —SiR₂R₃R₄, in which R₂, R₃ and R₄ each independently being a (C₁-C₄) alkyl group; R_(1b), R_(2b), R_(3b) and R_(4b), being the same or different, each independently being: a hydrogen atom; a halogen atom; a (C₁-C₆) alkyl group; a —N═CHR₅ group, in which R₅ is a (C₁-C₄) alkyl, pyridyl or phenyl group; a —C≡C—R₆ group, in which R₆ is a hydrogen atom, a (C₁-C₄) alkyl, tri (C₁-C₄) alkylsilyl, or phenyl group; a nitro group, or a —N═C—R₅ or —NR₇R₈ group, in which R₇ is hydrogen atom and R₈ is a hydrogen atom or a group —C(O)R₅ with R₅ chosen from a (C₁-C₄) alkyl, pyridyl or phenyl group; it being understood that, when at least one of the R_(1a), R_(2a), R_(3a) et R_(4a) groups is a methyl group, the others are a hydrogen atom or when R_(1a)═R_(2a)=R_(3a)=R_(4a) and are either a (C₂-C₄) alkyl or a hydrogen atom, then the at least one of the R_(1b), R_(2b), R_(3b) or R_(4b) substituents is different from hydrogen or from the tert-butyl group. 4- Metal (II) complexes according to claim 2, wherein: R_(1a), R_(2a), R_(3a) and R_(4a), being the same or different, each is independently: a hydrogen atom; a (C₁-C₁₂) alkyl group; a (C₁-C₁₂) alcenyl group, or a —SiR₂R₃R₄, in which R₂, R₃ et R₄ each independently being a (C₁-C₄) alkyl group; R_(1b), R_(2b), R_(3b) and R_(4b), being the same or different, each independently being: a hydrogen atom; a halogen atom; a (C₁-C₆) alkyl group; a —N═CHR₅ group in which R₅ is a (C₁-C₄) alkyl, pyridyl or phenyl group; a —C≡C—R₆ group, in which R₆ is a hydrogen atom; a (C₁-C₄) alkyl, tri(C₁-C₄)alkylsilyl, phenyl, or a group having the formula:

where R₁₆ is a hydrogen atom or a phenyl, eventually substituted in para by a (C₁-C₆) alkyl group; a nitro group, or a —NR₇R₈ group, in which R₇ is a hydrogen atom and R₈ is a hydrogen atom or a —C(O)R₅ group with R₅ being chosen from a (C₁-C₄) alkyl, pyridyl or phenyl group; it being understood that, when at least one of the R_(1a), R_(2a), R_(3a) or R_(4a) groups is a methyl group, the others are a hydrogen atom or when R_(1a)=R_(2a)=R_(3a)=R_(4a) and are either a (C₂-C₄) alkyl or a hydrogen atom, then the at least one of the R_(1b), R_(2b), R_(3b) or R_(4b) substituents is different from hydrogen or from the tert-butyl group. 5- Metal (II) complexes according to one of claims 1 to 4, wherein at least one of the R_(1b), R_(2b), R_(3b) or R_(4b) substituents is a nitro, —N═CHR₅ or —NR₇R₈ group, wherein R₇ is a hydrogen atom and R₈ is a hydrogen atom or a —C(O)R₅ with R₅ being chosen from among a (C₁-C₄) alkyl, pyridyl or phenyl group. 6- The metal (II) complexes according to one of claims 1 to 6, wherein the thiacalix[4]arene is of formula (Ia):

wherein R_(1a), R_(2a), R_(1b) et R_(2b) are as defined in claims 1 to
 5. 7- The metal (II) complexes according to claim 6, wherein R_(1a) is a hydrogen atom or a (C₁-C₁₂)alkyl or (C₁-C₁₂)alcenyl group and R_(2a) is a hydrogen atom or a (C₁-C₁₂) alkyl, (C₁-C₁₂) alcenyl, —SO₂—R₁ or —SiR₂R₃R₄ group; R₁, R₂, R₃ et R₄ being such as defined for (1) in claim 1 or
 2. 8- The metal (II) complexes according to one of claims 1 to 7, wherein the thiacalix[4]arene is of formula (Ib):

wherein R_(1a), R_(2a) and R_(1b) are as defined in claims 1 to
 7. 9- The metal (II) complexes according to one of claims 1 to 8, wherein the thiacalix[4]arene is of formula (Ic):

wherein R₁₈ and Rib are as defined in claims 1 to
 8. 10- The metal (II) complexes according to claim 1, wherein the thiacalix[4]arene is chosen from the group comprising: 5,11,17,23-tetraiodo-25,26,27,28-tetrahydroxythiacalix[4]arene; 5,11,17,23-tetrabromo-25,26,27,28-tetrahydroxythiacalix[4]arene; 5,11,17,23-tetra(tert-butyl)-25-propoxy-26,27,28-trihydroxythiacalix[4]arene, 5,11,17,23-tetra(tert-butyl)-25,27-di(tert-butyldimethylsiloxy)-26,28-di-hydroxythiacalix[4]arene, 5,11,17,23-tetra(tert-butyl)-25,26,27,28-tetrahexyloxythiacalix[4]arene, 5,11,17,23-tetrakis(phenylazo)-25,26,27,28-tetrahydroxythiacalix[4]arene, 5,11,17,23-tetrakis(4-nitrophenylazo)-25,26,27,28-tetrahydroxythiacalix[4]arene, 5,11,17,23-tetra(tert-butyl)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene, 5,11,17,23-tetranitro-25,26,27,28-tetrahydroxythiacalix[4]arene, tetrachlorhydrate de 5,11,17,23-tetramino-25,26,27,28-tetrahydroxy-thiacalix[4]arene, 25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene, 25,27-di(tert-butyidimethylsiloxy)-26,28-dihydroxythiacalix[4]arene, 5,11,17,23-tetrakis(phenylazo)-25,27-di(4-toluenesulfonyloxy)-26,28-di-hydroxythiacalix[4]arene, 5,11,17,23-tetrakis(4-nitrophenylazo)-25,27-di(4-toluenesulfonyloxy)-26,28-dihydroxythiacalix[4]arene, 5,17-diiodo-25,26,27,28-tetrahydroxythiacalix[4]arene, 5,17-dibromo-25,26,27,28-tetrahydroxythiacalix[4]arene, 5,11,17,23-tetra(4-pyridylimino)-25,26,27,28-tetrahydroxythiacalix[4]arene, 5,11,17,23-tetra(phenylethynyl)-25,26,27,28-tetrahydroxythiacalix[4]arene, 5,11,17,23-tetraethynyl-25,26,27,28-tetrahydroxy-thiacalix[4]arene. 11- The metal (II) complexes according to one of claims 1 to 10 having a transition metal. 12- The metal (II) complexes according to claim 11 with copper, silver, zinc, lead or platinum. 13- The metal (II) complexes according to claim 12 with copper, zinc or nickel. 14- Utilization of a thiacalix[4]arene (I) or of a metal (II) complex such as defined in one of claims 1 to 13 for the manufacture of materials having optic limiter properties. 15- The utilization according to claim 14 for manufacturing of materials for protection against lasers. 16- Utilization of a metal (II) complex as defined in claim 13 for manufacturing of thermochrome materials. 17- A method for preparing a thiacalix[4]arenes having formula (I) as defined in claim 5, wherein at least one of the R_(1b), R_(2b), R_(3b) or R_(4b) substituents is a nitro, —N═CHR₅ or —NR₇R₉ group, wherein R₇ is a hydrogen atom and R₈ is a hydrogen atom or a —C(O)R₅ group with R₅ being chosen from the group comprising a (C₁-C₄) alkyl, pyridyl or phenyl group, characterized in that: a) if R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are a nitro group, the compound (1) is obtained by nitration of the corresponding thiacalix[4]arene, in which said R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are a hydrogen atom, by the action of the nitrogen dioxide or the dinitrogen tetroxide in the presence of an etherized solvent; b) if R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are an amino group, the compound (1) is obtained by reduction of the respective compound (I), in which said group(s) R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are a nitro group; c) if R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are a —N═CHR₅ group, R₅ being a (C₁-C₄) alkyl, phenyl or pyridyl group, the compound (I) is prepared using the respective compound (I), in which said R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are an amino group, by the action of an aldehyde R₅—CHO or a ketone R₅—C(O)R₉, R₅ and R₉, being the same or different, independently being one of the other, a (C₁-C₄) alkyl, pyridyl or phenyl group; d) if R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are a —NHC(O)R₅ group, in which R₅ is a (C₁-C₄) alkyl, pyridyl or phenyl group, the compound (I) is obtained using the respective compound (1), in which R_(1b), R_(2b), R_(3b) and/or R_(4b) is/are an amino group, by the action of the acid halogenide Hal-C(O)R₅, in which Hal is a halogen atom and R₅ and is as hereinbefore defined. 18- The method according to claim 17, wherein at paragraph a), the nitrogen dioxide or the nitrogen tetroxide is formed in situ in the presence of aluminum trichloride and potassium nitrate. 19- The method according to claim 17 or 18, wherein at paragraph a) the nitrogen dioxide or the nitrogen tetroxide is in the form of a complex with the etherized solvent. 20- The method according to one of claims 17 to 19, wherein at paragraph a) diglyme, triglyme, tetraglyme or a crown ether is used as the etherized solvent. 